United States Patent Office Patented Jan
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3,071,593 United States Patent Office Patented Jan. 1, 1963 2 3,071,593 O PREPARATION OF AELKENE SULFES Paul F. Warner, Philips, Tex., assignor to Philips Petroleum Company, a corporation of Delaware wherein each R is selected from the group consisting of No Drawing. Filed July 27, 1959, Ser. No. 829,518 5 hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl 8 Claims. (C. 260-327) groups having 1 to 8 carbon atoms, the combined R groups having up to 12 carbon atoms. Examples of Suit This invention relates to a method of preparing alkene able compounds are ethylene oxide, propylene oxide, iso sulfides. Another aspect relates to a method of convert butylene oxide, a-amylene oxide, styrene oxide, isopropyl ing an alkene oxide to the corresponding sulfide at rela O ethylene oxide, methylethylethylene oxide, 3-phenyl-1, tively high yields without refrigeration. 2-propylene oxide, (3-methylphenyl) ethylene oxide, By the term "alkene sulfide' as used in this specifica cyclohexylethylene oxide, 1-phenyl-3,4-epoxyhexane, and tion and in the claims, I mean to include not only un the like. substituted alkene sulfides such as ethylene sulfide, propyl The salts of thiocyanic acid which I prefer to use are ene sulfide, isobutylene sulfide, and the like, but also 5 the salts of the alkali metals or ammonium. I especially hydrocarbon-substituted alkene sulfides such as styrene prefer ammonium thiocyanate, sodium thiocyanate, and oxide, and in general all compounds conforming to the potassium thiocyanate. These compounds can be reacted formula with ethylene oxide in a cycloparaffin diluent to produce 20 substantial yields of ethylene sulfide and with little or S no polymer formation. - It is essential in my invention that the reaction diluent be a cycloparaffin having from 4 to 10 carbor atoms and preferably 5 to 8 carbon atoms per molecule. Examples wherein each R is selected from the group consisting of of suitable cycloparaffins are cyclohexane, cyclobutane, hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl 25 methylcyclopropane, cyclopentane, methylcyclopentane, groups, said R groups having up to 8 carbon atoms in methylcyclohexane, ethylcyclopentane, 1,1-dimethylcyclo dividually and up to 12 carbon atoms combined. pentane, 1,2-dimethylcyclopentane (both cis and trans), Alkene sulfides are having increasing importance in 1,3-dimethylcyclopentane (both cis and trans), cyclo the synthesis of organic sulfur compounds. They can octane, ethylcyclohexane, 1,3-dimethylcyclohexane (both also be employed as insecticides or fungicidal agents as 30 cis and trans), 1-isopropyl-4-methylcyclohexane, and the described in U.S. Patent 2,225,573. These compounds like. can be prepared from the corresponding alkene oxides by The reaction between the ethylene oxide and the thio reaction with salts of thiocyanic acid in the presence of cyanate occurs readily in the cycloparaffin diluent at a such solvents as water, alcohol, and ether or mixtures temperature in the range of about 50 to 150 F. Elevated thereof. In such processes refrigeration is necessary for 35 pressures are not necessary unless the reaction diluent appreciable yields of the desired sulfide; generally, the selected requires an elevated pressure to maintain a liquid reaction temperature being about -5 to -10° C. phase at the temperature chosen to conduct the reaction. I have discovered quite unexpectedly that alkene Sul Generally, a pressure slightly above atmospheric is used, fides can be prepared by the reaction between an alkene for example, about 1 to 5 p.s.i.g. The alkene sulfide is oxide and a salt of thiocyanic acid without the necessity 40 preferably separated from the reaction diluent following of refrigeration if the reaction is conducted in a diluent completion of the reaction by distillation. It is therefore of cycloparaffin. Generally, the cycloparaffin should desirable to select a diluent which has a boiling point suffi have from 4 to 12 carbon atoms per molecule and prefer ciently different from that of the desired alkene sulfide to to use as a diluent for the reaction of my invention a permit a good separation. cycloparaffin having from 5 to 8 carbon atoms per 45 To further illustrate the advantages of my invention, molecule. the following example is presented which should be It is an object of my invention to provide a method of interpreted as being typical and not unduly limiting. preparing alkene sulfides. Another object is to provide a process by which alkene sulfides can be prepared from EXAMPLE the corresponding alkene oxides without the necessity of 50 Ethylene oxide and ammonium thiocyanate were re refrigeration. Still another object of my invention is to acted in several runs employing a variety of solvents. In improve the yield of alkene sulfide which can be obtained each case the reaction temperature was about room tem by reacting a salt of thiocyanic acid with an alkene oxide perature or slightly above. The ethylene sulfide was re at about room temperature. Other objects, advantages covered in those runs with measurable yields by distilla and features of my invention will be apparent to those tion. Ethylene sulfide has a boiling point of 130 F. and skilled in the art from the following discussion. can be separated from cyclohexane at atmospheric pres The alkene oxides which can be employed in my inven sure to yield a product of better than 95 percent purity. tion for the preparation of alkene sulfides are those com The data of these runs are presented in the following pounds which have the general formula 60 table. 3,071,593 3. 4. Table I Run No. A. B C D G H Solvent------------ Cyclohexane Cyclohexane Cyclohexane Water Methanol n-Heptane Soltrol 1301 Run conditions: Temp., F--- 88-00 90 85 285-40 85-100 90-08 Pressure, P.Sig------- 3 2 1. 2.5 0.0 5 5 Reaction time, hrs---- 2.5 1.2 2 4. Charge: G. Moles G. Moles G. Moles G. Moles Ammonium thiocyanate- 152 2 602 7.9 568 7.48 152 2 Ethylene oxide-------- 56 3.1 654 14.9 454 10.3 260 Solvent------- 400 - - - - - - 2,780 -------|3,040 ------- 150 Products: 260 Soltrol 130 (Trademark). A mixture of highly branched paraffinic hydrocarbons boiling over the range of about 335 F. to 410° F. 2 No heat applied. Temperature rise was from exothermal reaction. 8 Mn). Eg. Added H2S to reactor effluent of pH 8. Product consistency of thick gravy and looks like uncoagulated rubber. Recovered 52g. polymer from it. 5 Distillation of the reactor effluent yielded 20 ml of material boiling from 119°F. to 133° F. Reactor product solidified on cooling; after water washing to remove salts, 36 g. of waxy water insoluble polymer was recovered. Although complete material balances were not made, it is a safe assumptionNOTE.-Leaders that most (------) of the ethylenein figure columnsoxide unaccounted indicate that for datawent was to polymer not obtained. which was entrained with the ammonium cyanate reactor product. It can be seen from the above data that the conven wherein each R is selected from the group consisting of tional solvents, water and methanol, do not permit satis hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl factory yields of ethylene sulfide at ambient temperatures groups having 1 to 8 carbon atoms, the combined R whereas the yields when cyclohexane was employed as groups having up to 12 carbon atoms, with a thiocyanate the diluent were unexpectedly high. It is also noted that 30 selected from the group consisting of ammonium thio acyclic hydrocarbons such as n-heptane and Soltrol 130 cyanate and alkali metal thiocyanates, in a reaction dilu did not provide appreciable yields of ethylene sulfide. ent of from 2 to 10 volumes of cycloparaffin having from As will be evident to those skilled in the art, various 5 to 8 carbon atoms per molecule per volume of re modifications of this invention can be made, or followed, actants at a temperature of about 50 to 150 F., and in the light of the foregoing disclosure and discussion, 35 separating the alkylene sulfide reaction product from the without departing from the spirit or scope thereof. cycloparaffin by distiliation. I claim: 4. The process of claim 3 wherein said compound is 1. A process for making alkene sulfides which com ethylene oxide. prises contacting a compound having the formula 5. The process of claim 3 wherein said compound is 40 propylene oxide. lo 6. The process of claim 3 wherein said compound is R;04 Sor, isobutylene oxide. wherein each R is selected from the group consisting of 7. The process of claim 3 wherein said reaction dilu hydrogen, alkyl, aryl, alkaryl, aralkyl and cycloalkyl ent is cyclohexane. groups having 1 to 8 carbon atoms, the combined R 45 8. A process for making ethylene sulfide, which com groups having up to 12 carbon atoms, with a compound prises contacting ethylene oxide in a cyclohexane diluent selected from the group consisting of ammonium thio with ammonium thiocyanate at about 50 to 150 F. and cyanate and alkali metal thiocyanates in a reaction diluent of cycloparaffin having 5 to 8 carbon atoms per molecule separating the ethylene sulfide product from the cyclo at a temperature of about 50 to 150 F. 50 hexane by distillation. 2. The process of claim 1 wherein said reaction diluent is cyclohexane. References Cited in the file of this patent 3. A process for making alkene sulfides which com UNITED STATES PATENTS prises contacting a compound having the formula 2,094,837 Dachlauer -------------- Oct. 5, 1937 O 2,094,914 Dachlauer et al. --------- Oct. 5, 1937 R-04 ScR, 2,183,860 Coltof---------------- Dec. 19, 1939 .